Fluorinated tris(pyridyl)borate ligand support on coinage metals

Abstract

A useful ligand involving three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized in coinage metal chemistry. This tris(pyridyl)borate serves as an excellent...

Bonding and 13C‐NMR properties of coinage metal tris(ethylene) and tris(norbornene) complexes: Evaluation of the role of relativistic effects from DFT calculations

“…The coinage‐metal alkene interaction is evaluated by the interaction energy (Δ E int ) related to the formation of each M‐(CC) bond in terms of the Energy Decomposition Analysis (EDA) scheme of Ziegler and Rauk (Table 2). 55,58,78 This approach provides insights into the nature of the metal–ligand interaction related to the bonding scheme and the different stabilizing terms retaining the efficient alkene coordination for the studied species 79–82 . For [M(η 2 ‐C 2 H 4 ) 3 ] + series, the Δ E int amounts to −37.3, −26.3, and −41.8 kcal mol −1 for Cu, Ag, and Au complexes, respectively (Table 2) per alkene, illustrating a more favorable bonding situation according to Au > Cu > Ag, in agreement with the other reported coinage‐metal species featuring metal‐carbon bonds, 47 including coinage‐metal carbenes 39–43 …”

“…55,58,78 This approach provides insights into the nature of the metal-ligand interaction related to the bonding scheme and the different stabilizing terms retaining the efficient alkene coordination for the studied species. [79][80][81][82] For [M(η 2 -C 2 H 4 ) 3 ] + series, the ΔE int amounts to À37.3, À26.3, and À41.8 kcal mol À1 for Cu, Ag, and Au complexes, respectively (Table 2) per alkene, illustrating a more favorable bonding situation according to Au > Cu > Ag, in agreement with the other reported coinage-metal species featuring metal-carbon bonds, 47 including coinage-metal carbenes. [39][40][41][42][43] In order to evaluate the variations in bonding along with the group 11 triad for the alkene coordination, the ΔE int can be further decomposed into several chemically meaningful terms within the EDA framework, 61 according to:…”

Development of a novel scorpionate ligand with 6-methylpyridine and comparison of the structural and electronic properties of nickel(ii) complexes with related tris(azolyl)borates

“…Anionic facially-capping tris(azolyl)borate ligands, so-called scorpionate ligands, 1 [BL 3 X] − (L = nitrogen atom donors such as pyrazole, 1,2 oxazoline, [3][4][5][6] pyridine, [7][8][9][10][11][12][13] or imidazole; 14 X = H, phenyl, alkyl, alkoxide, etc. ), have been extensively utilized to synthesize various coordination compounds.…”

“…Very recently, 4-tert-butylphenyltris(6-trifluoromethyl-2-pyridyl)borate, [PhB(Py CF3 ) 3 ] − (= Tpy CF3 ), has been reported. 12,13 In the ethylene complexes of Cu(I), Ag(I) and Au(I) with this fluorinated ligand, Tpy CF 3 coordinates to the metal center in the κ 2 but not κ 3 fashion. 12 Tpy CF3 also coordinates in the κ 2 fashion with the carbonyl complexes of Cu(I) and Ag(I), whereas the related 3-trifluoromethylpyrazolyl ligand, [PhB(Pz CF3 ) 3 ] − , coordinates to the copper(I) center with κ 3 fashion in the carbonyl complex.…”

“…12,13 In the ethylene complexes of Cu(I), Ag(I) and Au(I) with this fluorinated ligand, Tpy CF 3 coordinates to the metal center in the κ 2 but not κ 3 fashion. 12 Tpy CF3 also coordinates in the κ 2 fashion with the carbonyl complexes of Cu(I) and Ag(I), whereas the related 3-trifluoromethylpyrazolyl ligand, [PhB(Pz CF3 ) 3 ] − , coordinates to the copper(I) center with κ 3 fashion in the carbonyl complex. 13 Therefore we have designed a moderately hindered tris( pyridyl)borate ligand, namely phenyltris(6-methyl-2-pyridyl)borate, [PhB(Py Me ) 3 ] − (= Tpy Me ; 1), in which an electron-donating methyl group is introduced at the 6-position of the pyridyl group to construct a bowl-shaped cavity surrounding the metal center for preventing the formation of a homoleptic inert complex.…”